N-bromobutanimide → HCID 14677374, compound

HRID 1074287Notes

Reaction equation

HRID 1074287 reaction equation
[C:1]([O:4][C@@H:5]1[C@@:32]2([CH3:33])[C:9](=[CH:10][CH2:11][C@@H:12]3[C@@H:31]2[CH2:30][CH2:29][C@@:28]2([CH3:34])[C@H:13]3[CH2:14][CH2:15][C@@H:16]2[C@H:17]([CH3:27])[C@H:18]([O:25][CH3:26])[CH2:19][CH2:20][C:21]([OH:24])([CH3:23])[CH3:22])[CH2:8][C@@H:7]([O:35][C:36](=[O:38])[CH3:37])[CH2:6]1)(=[O:3])[CH3:2].BrN1C(=O)CCC1=O>C(Cl)(Cl)(Cl)Cl>[C:1]([O:4][C@@H:5]1[C@@:32]2([CH3:33])[C:9](=[CH:10][CH:11]=[C:12]3[C@@H:31]2[CH2:30][CH2:29][C@@:28]2([CH3:34])[C@H:13]3[CH2:14][CH2:15][C@@H:16]2[C@H:17]([CH3:27])[C@H:18]([O:25][CH3:26])[CH2:19][CH2:20][C:21]([OH:24])([CH3:22])[CH3:23])[CH2:8][C@@H:7]([O:35][C:36](=[O:38])[CH3:37])[CH2:6]1)(=[O:3])[CH3:2]

Participants

4

Reactant 2

HCID 67184N-bromobutanimideHCID 14428815HCID 14428815, compound

Product 1

HCID 14677374HCID 14677374, compoundYield 17%

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Procedure

25.6 mg of (22R)-1α,3β-diacetoxy-25-hydroxy-22-methoxy-cholest-5-en (Vb1) was dissolved in 2 ml of carbon tetrachloride, the mixuture was refluxed under heating under an argon gas stream atmosphere, and 12 mg of N-bromosuccinimide was added to the mixture. After refluxing for 25 minutes, the mixture was cooled with ice-water, and the insoluble material was removed by filtration. The filtrate was concentrated under reduced pressure, and the residue was dissolved in 5 ml of tetrahydrofuran, and after adding thereto catalytic amount of tetra-n-butyl ammonium bromide, the mixture was stirred for 1 hour under an argon gas stream atmosphere. To the reaction mixture was added 0.17 ml of tetra-n-butyl ammonium fluoride (1M solution), and the mixture was stirred for 30 minutes at room temperature. The mixture was diluted with ethyl acetate, washed with 2N hydrochloric acid, saturated aqueous sodium hydrogen carbonate, and water, successively, and dried over sodium sulfate. The residue was dissolved in 10 ml of acetone, and after adding thereto about 5 mg of p-toluenesulfonic acid, the mixture was stirred overnight at room temperature under an argon gas stream atmosphere, under dark condition. The reaction mixture was diluted with ethyl acetate, washed with water, and dried over magnesium sulfate. The solvent was distilled away, and the residue was purified by using a column (Merck Company. Lichroprep RP-8, size A, solution; 15% watermethanol) to give 4.33 mg of (22R)-1α,3β-diacetoxy- 22-methoxy-cholest-5,7-dien-25-ol (VIb1).

Workup

  1. temperaturethe mixuture was refluxed
  2. additionwas added to the mixture
  3. temperatureAfter refluxing for 25 minutes
  4. customthe insoluble material was removed by filtration
  5. concentrationThe filtrate was concentrated under reduced pressure
  6. dissolutionthe residue was dissolved in 5 ml of tetrahydrofuran
  7. additionafter adding
  8. additionTo the reaction mixture was added 0.17 ml of tetra-n-butyl ammonium fluoride (1M solution)
  9. stirringthe mixture was stirred for 30 minutes at room temperature
  10. additionThe mixture was diluted with ethyl acetate
  11. washwashed with 2N hydrochloric acid, saturated aqueous sodium hydrogen carbonate, and water
  12. dry with materialsuccessively, and dried over sodium sulfate
  13. dissolutionThe residue was dissolved in 10 ml of acetone
  14. additionafter adding
  15. stirringabout 5 mg of p-toluenesulfonic acid, the mixture was stirred overnight at room temperature under an argon gas stream atmosphere
  16. additionThe reaction mixture was diluted with ethyl acetate
  17. washwashed with water
  18. dry with materialdried over magnesium sulfate
  19. distillationThe solvent was distilled away
  20. customthe residue was purified

Sources & evidence

ORD record
ord-26e675c54a9148cf9697dfc3da75ad93
Source dataset
uspto-grants-1990_11
Patent number
US04973721

Reaction notes

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